Production of anthraquinone derivatives



Patented Aug. 29, 1933 No Drawing. Application September 1932,

Serial, No. October'ZZ, 1931 635,608, and" in; o Britain 3 19 Claims. (01. 260-60) This invention relates to the p 'oductionof anthraquinone derivatives. v I

It is an ohjectofithis invention to provide a novel and efficient process for the manufacture of l-amino-2-chloro-anthraquinoneL i It is a further object of this invention to produce novel intermediate compounds, more'particularly, 2-chloro-l-aryl sulfonainido anthraquinones, which are adapted to be converted ef- 10, ficiently into1-ainino2-chloro-anthraquinoneby the simple step of hydrolysis. r V

Other and further important objects of this invention-will appear asthe description. proceeds. r According to our invention '1,2-dichloro-anthraquinone is condensed with an arylsulfonomide, e. p toluenesulfonamide, in the presence of an acid absorber and a copper catalyst under conditions which lead to substantially complete replacement of the a-chloro atom; thus, the condensation may be effected in a' medium inwhich the 2 -ch1oro 1 arylsulfonamido anthraquinone compound produced is insoluble and is therefore.

removed from the sphere o ffacti'on by precipitae tion. The arylsuifonyl group may be subsequent ly removed from the product byhydrolysis'e. g, with sulfuric acid, and the hydrolyzed product may he purified by diluting the acid solution somewhat and filtering on precipitated impurities, the filtrate being finally fully diluted to U precipitate thedesired product;

In a preferred form of our invention ,1,2-di- It will be understood, however,-that this inven-- tion is susceptible of wide variations and modifi- 5 I cations without departing from the spirit'thereof.

, 4 The invention is illustrated but not limited by the following examples, in which the parts are by weight. 7

Example 1 I V 60 parts of 1,2-dichloro-anthraquinone are dissolved in 300 parts of o-dichlorobenzene at the boil. 46 parts of potassium carbonate (99100%), 0.6 parts of copper acetate and 0.9 parts of cuprous chloride are then addedand finally while, still boiling gently, 60 parts ofp toluenesulfonamide are added in small portions at a time dur- 46 parts of water, and the mixture 'ilteredat mg m hours;- At as end of this time the tem? perature is kept between 174-178 C; for l5-hours.

The product is allowed to coolisomewhat, steamed to remove the 'o dichlorobenzene, filtered, and the residue Washed ,with water-and dried.

Err ample 2 i 86 "parts of'the product'of Example 1 are added to 350 partsof 100%' sulfuric acid, mixed cold 5 and heated-to 100-C; for one hour. 'I'he tem- .perature, is then let down to 80 6;; sufficient water is added to reduce the acid strength to 80% sulfuricacid, and the mixture is filtered at8'0 .C. The filtrate is poured'into an excess of waterand the 2-chloro-l aminoeanthraquinone is obtained in very good'purity and almost theoretical yield. The 'filtration at' 86 C. removes traces of un-j changed '1,2 dichloro 'anthraquinone if these are present; i""" 3 40 parts of 1,2edichloro anthraduinone are dissolved in ,300partsof o-dich1orohenzene at v the boil. ,40 a parts of potassiumgcarbonate (997100721), 0.4 parts of; copper Lacetate and ;0, 6 parts of cuprous chlorideare added, fol1owed by I 40, parts. of o-toluenesulfonamide in, small"p r-; tions over 3 hours, The temperature is" then' kept at 1744-78" C..for l2 hours and thensteamed to remove ordichlorobenzene, The solid-is isolated by filtration, washed thoroughly With-water anddried. Yield60 parts. I v

30 parts of the productof Example 3 are dissolved in'1'2 0 parts of 97,% sulfuric acid in thecold and heated to 100? C. for lfhour, The temperature is lowered to 80 Gland the charge diluted to"70% sulfuric acid bythe addition of 8085 C. The residue consists. of a small amount of unchanged 1,2-dichloro-arithraquinone. The

filtrate is poured into excesswater and the 2-,. chloro-1-amino anthraquinone"isolated by filtra- Having now particularly described-and; ascer- I tion, washing and drying.I"fYield l8 partscf j tained the nature of our said invention, and in what manner the same is tobe performed,' we

declare that What we claimis:

'1. A process for producing 1-ainino-2-ch1oroanthroquinone which comprises reacting'upon s 1,Z-dichloro-anthraquinhne with an. aryl-sulfonamide to produce 7 1 ary1sulf0namido-2-chloro 7 j anthraquinone, and hydrolyzing th'ela'tter to split off the aryl-sulfonyl group. a g 2,; 1

PATEN I arylsulfonamido-2-chloro-ahthranquinone is in- ,soluble, recovering the latter, reacting upon, the

same with concentrated sulfuric acid, and finally recovering the 1-amino-2-chloroanthraquinone formed by successive dilution and filtering.

4.-A process for producing 1-amino-2-chloroanthraquinone which comprises reacting jupon l,2-dichloro-anthraquinone with an aryl-sulfonamide in a medium in which the resulting 1- arylsulfonamido-Z-chloro-anthraquinone is insoluble, recovering the latter, reacting upon the same with concentrated sulfuric acid, and drowning the reaction mass in water to precipitate 1- amino-2-chloro-anthraquinone.

5. In the process of preparing 1'-amino-2- chloro-anthraquinone, the step which comprises reacting upon 1,2-dichloroanthraquinone with an aryl-sulfonamide to produce l-arylsulfonamido-Z-chloro-anthraquinone.-

-6.,In the process of preparing l-amino-Z- chloro-anthraquinone, the step which coma prises reacting upon 1,2-dichloro-anthraquinone with a :toluene-sulfonamide to produce 1 -tol-- uenesulfonamido-Z-ch1oro-anthroquinone.-

7. In the process of preparing 1-amino 2- chloro-anthraquinone, the steprwhich comprises reacting upon 1,2-dichloro-anthraquinone withp-toluene-sulfonamide to produce, l-p toluenesulfonamido-2-chloro-anthraquinone.

8. In the process of preparing l-aminO-Z- chloro a'nthraquincne, the step which comprises reacting upon l,2 dichloro-anthraquinone with o-toluene-sulfonamide to produce 1-o-toluen'e sulfonamido-2-chloro-anthraquinone.

9. The, process of preparing a l-arylsulfon amido-2-chloro-anthraquinone which comprises reacting. 1,2-dichloro-anthraquinone with an aryl-sulfonamide in a medium in'which the resulting compound is insoluble.

10..The process of preparing a l-arylsulfonamide-2-chloro-anthraquinone which comprises reacting 1,Z-dichloro-anthraquinone with an aryl-sulfonamide in the presence of an acid absorber and a copper catalyst and in a medium in whichthe resulting compound is insoluble.

, 11. The process of preparing a l-toluenesulfonamido-2-chloro-anthraquinone which comprises reacting 1,2-dichloro-anthraquinone with a toluene-sulfonamide in a medium of o-dichloroben zene'and in the presence of an acid absorber and a copper catalyst.

12. The process of preparing l-p-toluenesulfonamido-Z-chloro-anthraquinone which com prises reacting 1,Z-dichloro-anthraquinone with ptoluene-sulfonamide in o-dichlorobenzene in the presence of an alkali-metal carbonate and a cuprous salt. v

13; The process of preparing l-o-toluenesulfonamide-2-chloro anthraquinone which comprises reacting l,2-dichloro-anthraquinone with 04501- uene-sulfonamide in o-dichlorobenzene in the presence of an alkaliemetal carbonate and a cuprous salt.

14. 'As a new compound, a l arylsulfonamidm 2-chloroanthraquinone. "'15. As a new compound, a 1-toluenesulfonamido-2-chloro-anthraquinone. I

16. As a new' compound, l-p-toluenesulfonamide-2-chloro-anthraquinone.

17. As a new compound, l-o-toluenesulfonamido-2-chloro-anthraquinone. I 18. In the process of producing "1-amino-2- chloro-anthraquinone, by the hydrolysis of a- 1- ary'lsulfonarnido-2-chloro-anthraquinone in a medium or" concentrated sulfuric acid, the step which comprises diluting, the reaction mass to a point where the 1-arnino-2 chloro anthraquinone is substantially soluble while the impurities are substantially insoluble, separatingthe clear solution from the precipitated impurities, and di-' luting the solution further, to precipitate 1-amino z-chloro anthraquinone. j I

' 19; In the process of producing .l-amino-Z- chloro-.-anthraquinoneby the hydrolysisof a 1- arylsulfonamido-2-chloro-anthraquinone in a medium of concentrated sulfuric acid, the step which comprises diluting the reaction mass to about'70-80% acid concentration, separating any' precipitate formed, drowning the-clear solution in water, and recovering the 1 precipitated 1- amino-2 chloro-anthraquinone.

ROBERT FRASER THOMSON. RHYS' JENKIN LOVELUCK. 

